Patent GB-981346-A (GB)
Title: Improvements relating to polythiomethylene compounds
IPC: C08G69/42
Filed: 1963-03-26
Abstract: Polythiomethylene sulphides have the general formula <FORM:0981346/C2/1> or <FORM:0981346/C2/2> where R is hydrogen, fluorine, iodine, chlorine, bromine, alkoxy, alkyl, cycloalkyl, phenyl or phenyl substituted by alkyl, alkoxy, halogen, aryloxy, cyano, or carbalkoxy or when taken together adjacent R's form a ring structure with the proviso that when adjacent R's are not taken together at least one of them must be hydrogen; X is hydrogen, hydroxy, cyano, <FORM:0981346/C2/3> isocyanato, chlorine, phenyl, hydrocarboaryl, <FORM:0981346/C2/4> , <FORM:0981346/C2/5> , <FORM:0981346/C2/6> , <FORM:0981346/C2/7> or OY where Y is alkyl; Q is alkylene, oxalkylene, aralkylene, arylene, arylene substituted by alkoxy, halogen, cyano or carbalkoxy; m is 0 or 1; n is at least 2 and such that -[CH2-S]n-has a number-average molecular weight of 93-316; G is an alkylene, oxaalkylene, or phenylene radical containing no more than 18 carbon atoms; and q is a cardinal number including 0 with the proviso that when q exceeds zero it indicates a number average molecular weight up to 5000 for the polythiomethylene sulphides.  When q = m = o the sulphides have the formula (1) <FORM:0981346/C2/8> and (2) <FORM:0981346/C2/9> These are prepared by reacting H-S-(CH2 -S)n-H with 2 mols. of (a) 2-norbornene to give (1) (b) an oxide <FORM:0981346/C2/100> to give (2) with X = OH; (c) a vinyl compound <FORM:0981346/C2/111> where X = H, <FORM:0981346/C2/122> CN or -C-OY to give (2) with X as specified; (a), (b) and (c) where X = H or <FORM:0981346/C2/133> being free radical catalysed and (c) where <FORM:0981346/C2/144> being base catalysed e.g. ammonia, piperidine and ammonium acetate.  When q = 0 and m = 1 the sulphides have the formula <FORM:0981346/C2/155> and are made by the free radical catalysed addition of 2 mols. of an olefin <FORM:0981346/C2/166> with one mol. of H-S-(CH2-S)n-H. Compounds in which q is at least 1 and m = o and those in which q is at least 1 and m = 1 are made by methods analogous to those given above.  While alpha-alpha1-azobisisobutyronitrile is the preferred free-radical catalyst, dialkyl peroxides, diacyl peroxides, substituted azoacetonitriles and -alkyl hydroperoxides as well as u-v radiation may be used.  A solvent may or may not be present e.g. benzene, saturated aliphatic hydrocarbons and alkyl primary alcohols. The mono-olefins used in making the compounds (B) may be ethylene, its analogues, styrene, 4 - methoxystyrene, 3 - chlorostyrene, allyl alcohol, methallyl alcohol, 10 - undecene-1 - al, methyl - 10 - undecenoate, acrylonitrile, 4 - pentene - 1 - carbonitrile, biallyl monepoxide, methyl acrylate and methyl methacrylate.  The products may be used as lube additives, antioxidants for petroleum fuels and in the case of the (B) compounds as chemical intermediates. Thus the -CN terminated can be reduced to -NH2 terminated, or treated with etherial lithium aluminium hydride to give the diamines.  The <FORM:0981346/C2/177> terminated may be hydrolysed with dilute mineral acid or reduced with lithium aluminium hydride to the HO-terminated polymer.  The mercapto-terminated polythiomethylene compounds H-S-(CH2-S)n-H have number-average molecular weights from 126 to about 350 and are prepared by reacting 1.75 to 10 mols. of liquid hydrogen sulphide with one mol. of formaldehyde, reacting the product at 100 DEG  C. with an aqueous non-oxidizing mineral acid to give a bis mercaptan HS(CH2-S)nH, where n is at least 2; contacting this with water at 100 DEG  C. raises the number-average molecular weight to about 350.  Several examples are given of the reaction of formaldehyde with hydrogen sulphide using various buffers in water to give mercapto-terminated polythiomethylenes in liquid or semi-solid form (IA-D,F,G and I,2A-E). The product may then be reacted with ethylene oxide I-H, G and J) or propylene oxide (2F) to give glycols or refluxed in the presence of alpha, alpha1-azodiiso-butyronitrile and (3A) allyl alcohol to give the glycol HO-CH2 -CH2-CH2-S-(CH2-S)n -CH2-CH2-CH2 -OH or (3D) methallyl alcohol to give <FORM:0981346/C2/188> or (3I) biallylmonoepoxide to give <FORM:0981346/C2/199> or (4A) a mixture of methallyl alcohol and 2-5-dimethyl-1.5-hexadiene to give a viscous liquid glycol or (4B) a mixture of allyl alcohol and the above diene to give a semi solid glycol or a mixture of (4C) methallyl or allyl alcohol (4D) with 1.5-hexadiene to give glycols.  The mercapto terminated polythiomethylenes may be further reacted under similar conditions with (7) vinyl acetate to give the diester <FORM:0981346/C2/200> or (8) N-allyl acetamide to give the diamide <FORM:0981346/C2/211> or (10) allyl glycidyl ether to give the bisepoxide <FORM:0981346/C2/222> or (11) allyl chloride to give the dichloride <FORM:0981346/C2/233> or (12) styrene to give <FORM:0981346/C2/244> or (15) ethyl vinyl ether to give <FORM:0981346/C2/255> or (16) acrylonitrile to give a cyano-terminated polythiomethylene compound. The catalyst may be replaced by irradiation when the reaction with allyl alcohol gives (5) the glycol <FORM:0981346/C2/266> Instead of the mercapto-terminated polythiomethylene there may be used as starting material bis(mercapto methyl)sulphide and this with (3B) allyl alcohol gives a glycol (3E) 10-undecylenyl alcohol to give the glycol  HO-(CH2)11-S-(CH2-S)n -(CH2)11-OH (3F) 1-hexene to give CH3(CH2)5-S-(CH2 -S)n-(CH2)5-CH3 (3G) methyl - 10 - undecenoate giving the ester <FORM:0981346/C2/277> which on reaction with ethanol-sodium hydroxide gives the acid <FORM:0981346/C2/288> (4E) allyl alcohol together with diallyl ether gives a glycol (4G) 1-5 hexadiene and methyl-10-undecenoate gives a diester (6) 3-methyl-3-butenol-1 gives the glycol <FORM:0981346/C2/299> (9) N-allyl acetamide gives a diamide with (13) alpha, alpha-dimethyl allyl isocyanate gives the compound O = C = N-C(CH3)2-(CH2)2 -S-(CH2-S)2-(CH2)2-O(CH3)2\t -N = C = O (14) the organic isocyanate <FORM:0981346/C2/300> (17A) CH2 = C-NCO to give a diisocyanate <FORM:0981346/C2/311> (17B) CH2 = CH-CH2-CH2-NCO gives the diisocyanate O = C = N-(CH2)4-S-(CH2-S)2 -(CH2)4-N = C = O and with an isocyanate <FORM:0981346/C2/322> to give the compound <FORM:0981346/C2/333>  The preparation of appropriate isocyanate intermediates is described.  In Example (13A) xylene, isoprene, isocyanic acid and ammonium p-toluene sulphonate are heated at 100 DEG  C. for 3 hours, the solid filtered off and the filtrate distilled and redistilled to give the alpha-alphadimethyl allyl isocyanate.  In Example 14(a) toluene, p-diisopropenyl benzene, isocyanic acid, ammonium tosylate and hydroquinone are agitated in an autoclave at 110-120 DEG  C. for 2 hours, filtered, distilled and redistilled to give an isocyanate containing 95% of <FORM:0981346/C2/344>  Specifications 731,071, 733,624, 790,725, 796,041, 796,044, 979,965, 801,023, 811,725 and 894,924 are referred to.ALSO:Polythiomethylene sulphides have the general formula <FORM:0981346/C3/1> <FORM:0981346/C3/2> where R is hydrogen, fluorine, iodine, chlorine, bromine, alkoxy, alkyl, cycloalkyl, phenyl or phenyl substituted by alkyl, alkoxy, halogen, aryloxy, cyano, or carbalkoxy or when taken together adjacent R's form a ring structure with the proviso that when adjacent R's are not taken together at least one of them must be hydrogen; X is hydrogen, hydroxy, cyano, <FORM:0981346/C3/3> isocyanato, chlorine, phenyl, hydrocarboaryl, <FORM:0981346/C3/4> or OY, where Y is alkyl; Q is alkylene, oxalkylene, aralkylene, arylene, arylene substituted by alkoxy, halogen, cyano or carbalkoxy; m is 0 or 1; n is at least 2 and such that -[CH2-S]n-has a number-average molecular weight of 93-316; G is an alkylene, oxa-alkylene, or phenylene radical containing no more than 18 carbon atoms; and q is a cardinal number including O with the proviso that when q exceeds zero it indicates a number average molecular weight up to 5000 for the polythiomethylene sulphides.  When q=m=O the sulphides have the formula (1) <FORM:0981346/C3/5> <FORM:0981346/C3/6> These are prepared by reacting H-S-(CH2-S)n -H with 2 mols. of (a) 2-norbornene to give (1) (b) an oxide <FORM:0981346/C3/7> to give (2) with X=OH; (c) a vinyl compound <FORM:0981346/C3/8> where X=H, <FORM:0981346/C3/9> CN or -C-OY to give (2) with X as specified; (a), (b) and C where X=H or <FORM:0981346/C3/100> being free radical catalysed and (c) where <FORM:0981346/C3/111> being base catalysed, e.g. ammonia, piperidine and ammonium acetate.  When q=O and m=1 the sulphides have the formula <FORM:0981346/C3/122> and are made by the free radical catalysed addition of 2 mols. of an olefin <FORM:0981346/C3/133> (or X-Q-CH=CH-R) with one mole of H-S-(CH2-S)n-H.  Compounds in which q is at least 1 and m=0 and those in which q is at least 1 and m = 1 are made by methods analogous to those given above.  While alpha-alpha1-azobisisobutyronitrile is the preferred free-radical catalyst, dialkyl peroxides, diacyl peroxides, substituted azoacetonitriles, and t-alkyl hydroperoxides as well as U.V. radiation may be used.  A solvent may or may not be present, e.g. benzene, saturated aliphatic hydrocarbons and alkyl primary alcohols. The mono-olefins used in making the compounds (B) may be ethylene, its homologues, styrene, 4-methoxy-styrene, 3-chlorostyrene, allyl alcohol, methallyl alcohol, 10-undecene -1-al, methyl-10-undecenoate, acrylonitrile, 4 - pentene - 1 - carbonitrile, biallyl monepoxide, methyl acrylate and methyl methacrylate.  The products may be used as lube additives, antioxidants for petroleum fuels and in the case of the (B) compounds as chemical intermediates. Thus the <FORM:0981346/C3/144> terminated polythiomethylene polymers give polymides with acid anhydrides, dicarboxylic acids or carbonyl terminated polymers, the -CH terminated can be reduced to -NH2 terminated, or treated with etherial lithium aluminium hydride to give the diamines, the -NH2 terminated